Manufacture of alcohol



May 26, 1953 N. GoLDsBRoUGH MANUFACTURE oF ALcoHoLs Filed oct. 15, 1949 www gz:

N xDlEmm |nventor: Leslie Newon Goldsbrough By: ml'mz u. .gg His Attorney Patented May 26, 1953 MANUFACTURE OF ALCOHOL Leslie Newton Goldsbrough, Thornton-le-Moors,

England, assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware Application October 15, 1949, `Serial No. 121,529 In Great Britain November 2, 1948 8 Claims.

This invention relates to the manufacture of alcohols which are sparingly soluble or insoluble in water and volatile with steam. It deals with animproved method for producing such alcohols by acid hydrolysis of mixtures of the corresponding acid and neutral esters of polybasic inorganic acids. It is also concerned with apparatus which is especially advantageous for carrying out this process.

The invention is thus concerned with the hydrolysis of mixtures containing at least one mono-ester and at least one polyester of a polybasic inorganic acid yielding an alcohol o-r mixture of alcohols which is sparingly soluble or insoluble in Water and volatile with steam', which ester mixture contains dilute aqueous acid sufcient in amount at least to initiate the hydrolysis -of the said acid ester. Elster mixtures of this type useful as starting materials for the new process may advantageously be obtained, for example, by reacting olenic hydrocarbons with polybasic inorganic acids such as sulfuric acid, phosphoric acid, boric acid and the like. The mixtures of monoand di-alkyl sulfates readily obtainable on a commercial scale by treating a higher olefn or a mixture of such clef-ins with strong sulfuric acid are convenient starting mixtures, particularly when derived from the vapor phase cracking of a petroleum wax, such as par- [mixtures containing at least one monoand at least one di-alkyl sulfate yielding an alcohol or alcohols which is or Iare sparingly soluble or insoluble in water Iand volatile in steam, andy containing dilute acid, such as dilute sulfuric acid, sufficient in amount at least to initiate the hydrolysis of the said mono-alkyl sulfate, Will be emphasized in the following description, and, for the sake of simplicity, these preferred starting mixtures will be hereinafter referred to as acid mixtures of monoand cli-alkyl sulfates. However. it will be understood that other analogous mixtures of monoand poly-esters from the same or other inorganic polybasic acids and other inonoolefinic hydrocarbons may be used in the invention in the same way.

Several diii'erent methods have been proposed forcarrying out the acid hydrolysis of alkyl sulfates. A tower-type hydrolyzer, for example, has been frequently used for the hydrolysis of diluted sulfation reaction mixtures. For the hydrolysisof lower alkyl esters, such methods are often quite satisfactory, but, in carrying out the acid hydrolysis of mixtures consisting of 0r containing higher monoand di-alkyl esters, diiiculties are encountered owing to the fact that the hydrolysis of the di-alkyl sulfate takes considerably longer than that of the mono-alkyl sulfate. If the residence time of the mixture in the reaction vessel is suniciently great for the hydrolysis of the bulk of the di-,alkyl sulfate to be completed, a substantial fraction of the potential yield of alcohol is liable to be lost owing to dehydration of alcohol to olefin by the acid, the concentration of which increases as the hydrolysis proceeds.

An important object of the present invention is to provide a process for hydrolyzing esters of polybasic inorganic acids which overcomes the foregoing difficulties. Another object is to provide a continuous method of hydrolyzing mixtures of higher alkyl mono-sulfate and di-sulfates, whereby increased yields of alcohol are obtained While at the same time the size of the reaction system required for a given throughput is reduced. Still another object is to provide an improved apparatus for carrying out reactions of this type in a more economical and efficient manner. Further objects and advantages of the invention will be apparent from the following description of the principles on which it is based and illustrative examples of some of its applications.

In accordance with the invention, the hydrolysis of acid mixtures of monoand di-alkyl sulfates, for example, is carried out in at least two reactors arranged in series, wherein the mixture is heated in the rst reactor to hydrolyze all o-r most of the mono-alkyl sulfate, and the reaction product passes into the second reactor and separates therein into two layers of which the lower .aqueous acid layer flows out of the reactor more rapidly than the upper oily layer, and the oily layer is subjected in the said reactor to steam distillation which removes the alcohol 4therefrom and brings about the hydrolysis of dialkyl sulfate and of any non-hydrolyzed monoalkyl sulfate which may still be present. The process is preferably carried out continuously with the reaction mixture owing directly from the rst to the second reactor.

The invention also comprises apparatus for carrying out the pro-cess described above, which comprises at least two reactors arranged in series for cascade flow, the rst reactor being adapted to be heated and having at its upper portion a discharge pipe leading to the second reactor, which latter reactor is provided with a steam injection pipe, an outlet for vapor, and a discharge pipe leading from the lower portion of the reactor and having an upright limb such that in operation the level of the liquid retained in the reactor iscontrolled mainly by the balance between the hydrostatic pressure due to the said liquid and that due to the liquid in the upright limb of the discharge pipe.

Owing to the more rapid now oi the aqueous acid layer from the second reactor, coupled with the removal of alcohol by steam distillation as it is formed, the residence time of the di-alkyl sulfate contained in the oilylaycr can be increased to the extent required for substantially complete hydrolysis, without the loss of any appreciable quantity of alcohol by dehydration. Moreover, owing to the relatively short residence time of the aqueous phase and to the continuous removal of alcohol, a long residence time of the di-alkyl sulfate can be achieved in a comparatively small reaction system.

Since, as in all continuous reaction systems, it is not usually practicable to ensure that every part of the fiuid has the same residence time, it is preferred to provide at least one further reactor in series with the aforesaid second reactor,

the function and mode ci operation of this third reactor and o any subsequent reactors being the same as that of the second reactor. The effluent from the nal reactor may advantageously be passed to a separating vessel to separate any residual oily phase consisting, for example, of polynfxers,A from the out-flowing dilute sulfuric acid.

The heat for the first reactor may conveniently be supplied by injecting steam into the reactor mixture. If desired, this steam may also be utilized for carrying out a limited steam distillation of thc alcohol produced in the reactor and of any steam-viclatile impurities which may be present. In this way the amount of steam distillation required in the second and subsequent reactors is reduced and the residence time of the oily layer in these reactors is increased. The amount of steam distillation which can be carried out in the first reactor is, however, limited by the tendency of the aqueous phase containing inonoealkyl sulfate to froth.

As has previously been mentioned, the alkyl sulfatos used as starting materials may conveniently be obtained by the sulfation of individual olelns or olerln mixtures, for example, olens containing from 5 to 12 carbon atoms in the molecule. The mixtures of monoand di-alkyl sulfatos derived from suliation of cracked wax distillates of 7 to 9 carbon atoms are especially useful. Since strong sulfuric acid is used for these sulfation reactions, the reaction product should be diluted with water before or as it is fed into the iirst hydrolysis reactor. Most preferably, the dilution is carried out so as to give a sulfuric acid concentration oi about 15% by weight (3. N acid) on an organic-free basis in the initial mixture to promote rapid hydrolysis of the mono-alkyl sulfates, and the acid concentration throughout the process is maintained below 30% by weight on an organic-free basis in order to minimize alcohol dehydration. y

It is also possible to start with mixtures of monoand di-alkyl sulfatos which are initially free from acid, and to form the acid mixture by the addition ci dilute acid to the mixture oi suliates before or as it is fed into the first hydrolysis reactor,

The invention will now be described in greater detail, by way of example reference being had to 4 the accompanying drawing which shows in diagrammatica form, also by way of example, a cascade apparatus for carrying out the invention.

Referring to the drawing, I0 represents a sulfation reactor. An olen or a mixture of olens obtained, `for example, from cracked paraln wax, is fed into the reactor I0 byline 4, and strong sulfuric acid is fed in by line 5. The reaction product, which consists mainly of a mixture ot monoeY and cli-alkyl. sulfates and sulfuric acid, together with polymers or other by-products and unconverted hydrocarbons, is fed by line 6 to line II into which a quantity of water is fed by line 'I. Pipe I I leads to the bottom of the first cascade reactor I. Steam is passed through the pipe I2 into the mixture in this reactor and heats the mixture so that the bull: of the mono-alkyl suliatc is hydrolyzed. In the example now being described, steam distillation of alcohol is not carried out in reactor If, the steam serving essentially as a source of heat. There may be a slight separation into layers in the reactor, as indicated in the drawing, the phases being denoted in the drawing by lined and dotted shading, as shown in the key. The contents ofreactor l pass through a pipe I3 into the second cascade reactor 2.

In reactor 2, the mixture separates readily into an upper oily layer and a lower acid aqueom layer. The lower aqueous layer, which consists mainly of sulfuric acid and water, runs through the reactor in a comparatively short time and iiows out through a pipe I4 leading from the bottom of the reactor. The upper oily layer, which consists mainly of alcohol, di-allzyl sulfate, polymers or other Icy-products and unconvcrted hydrocarbons, remains for a longer period in the reactor and is subjected to the action oi steam injected through a pipe l5. This steam acts as a source of heat and also serves to agitato the contents of the reactor, bringing the dilute acid into contact with the (ii-alkyl sulfate. The steam thus brings about hydrolysis of the di-alkyl sulfate and of any mono-alkyl sulfate which may have escaped hydrolysis in reactor i, the hydrolysis of the latter being completed as the aqueous phase passes down from the pipe ll through the oily phase. At the same time the steam acts as a distillation medium for removing the alcohol from the reaction Sphere, The mixed steam and alcohol vapors pass up the oiltake pipe I6 and into the vapor line I8.. via a. cyclone of liquid and returns them to reactor 2.

The pipe I4 leads into the third cascade reactor 3, Which is similar to reactor 2, being provided with a steam pipe I5.a, an oif-take pipe Ilay and a cyclone Ila. The composition of the layers formed in reactor 3 is similar to those in reactor 2, and the processes of hydrolysis and steam distillation are completed in the oily layer in reactor 3.

The vapor mixture in the vapor line, which contains any unconverted hydrocarbons and regenerated olens, in addition to the alcohol and water vapor,` is passed to a distillate separator I9 in which the vapor condenses and the condensate separates into a lower layer consisting of water and an upper layer containing the crude alcohol, that is to say the alcohol mixed with unconverted hydrocarbons and oleflns. Caustic soda may be injected by line 8 to remove traces of sulfur dioxide from the alcohol. The water fiows out through pipe 20 and the crude alcohol Il which removes entrained dropletsA is ledv through pipe 2I to a distillatlon'column for purification. Y

The eiilux from reactor 3 passes into a separator 22 and separates into a lower layer of dilute 6 usingl reactors each of capacity 17.5 gallons, the average residence time -of the whole reaction mixture is 40 minutes, and the average residence time of the oily layer in reactor 2 is 2.1 hours and Quctby redistiuauon. v q, p With the feed-rates given in the table, and 75 sulfuric acid which is removed by line 26 and an 5 in reactor 3 is 4.1 hours. These residence times, upper layer of polymer or other 'ny-products which are sufficient to insure complete hydrolysis which is taken off by line 21. of the di-alkyl sulfate, are thus obtained in a sys- The pipes I4 and I4a are provided with siphon tem having a `total capacity-of about 60 gallons. breakers 24, 24a, vented to atmosphere through If, on the other hand, a tower hydrolyzer workreuX condensers 25, 25a, only partly shown.f1o ing Without recycling were used, a capacity of The reactor I is also shown fitted with a reilux 2,000 'gallons would be required to give a fourcondenser 23, also only partly shown. hour residence time for the di-alkyl sulfate and, The residence times of the monoand di-alkyl moreover, diiiiculties would be encountered owing sulfates in the hydrolysis reactors are determined to frothing. by the rate of input `of the reactants, the sizes of v15 In the preferred cascade ow apparatus which the Vessels and the liquid levels maintained has been described, the levels of liquid in reactors therein, and, in the case of the di-alkyl sulfate, 2 and 3 are controlled mainly by the balance beby the rate of steam stripping of the other contween the hydrostatic pressure due to the oily stituents of the oily layer. As a general rule, a `layer in the reactor and that due to the aqueous residence time of about l5 to 60 minutes, pref-'2o phase (with a small supernatant oily layer) in -erably about 20 to 40 minutes, in reactor I will the vertical limb of theappropriate discharge eiect sufficient hydrolysis of the mono-esters pipe I4 or I4a. In order to prevent surging and when using a temperature within the preferred irregular operation, the feed rates of the reactrange of about 80 C. to 120 C. For hydrolysis ants and steam should be kept relatively conof the poly-esters in reactors 2 and 3, residence 25 stant. It is' also desirable to maintain a uniform times for the poly-esters should preferably total smooth discharge from the reactors 2 and 3. This at least3 hours and, more advantageously, be of can be achieved either by violent agitation in the order of 4 to 6 hours when using steam disor near the discharge outlets of the reactors so tillation at atmospheric pressure. With higher that the discharge consists of a dispersion of the or lower temperatures of hydrolysis such as ob- 30 oil phase in the aqueous phase, allowing separatained when steam distillation under superatmostion to take place in the discharge pipes i4 and -pheric or subatmospheric pressure is used, the I4a,.or by maintaining the liquid in the bottom of residence time for the poly-esters is reduced or the reactor quiescent, as shown in the drawing increased correspondingly. An illustration of lthat the oil phase is discharged aS a Steady 00nfeed rates for the various reactants and the re- 35 vtinuous stream of oil droplets which rise in the sulting output of the products at various stages acid in the discharge pipe. SteadncSS 0f Operaof the process, using apparatus so designed that tcn is alS assisted by PlOVdine that the Vapor the volume of liquid held in each of the reactors line i8 is such that there iS a 10W pressure drop I. 2 and 3 at the steady state is 17.5 gallons, is along its length. and that the discharge pipes I4 given by way of example in the following ta'ble, 40 and Ma are of suflicient cross-section to accomin which the gures represent; lbs/hour: modate small surges without appreciable varia- Reactor l0 Reactor 1 Reactor 2 Reactor 3 Component In Out In Out Out Out ollylafefnic hydrocarbons l6.0 6.0 6.0 6.0 0 0 olefin 198.0 o o l 3.5 o 0. Polymer (or other byproduct).... 24.5 24.5 24.5 24.5 24.5 Alcohol 41.4 11.8 0 Di-alkyl sulfate... 52.5 52.5 52.5 13.1 0 Aqueous Layer:

sulfuricacid 122.5 ses 66.5 105.0 118.1 122.5 water 9.3 9.a 352.3 345.9 343.2 342.5 Mono-alkylsulfate. 77.0 77.0 0 -0A 0 Steam Distillate:

Paraffnic hydrocarbons 6.0 leen. 14.8 0.7 2.1001101 47. s 17. 5

1 From a cracked wax distillate containing mainly C1 material.

Thus, the total yield of secondary heptyl alcohol tion of the hydrostatic balance, and by providing (B. P. 159 C.) was 64.8 lbs. per hour. the discharge pipes I4 and Ma with siphon break- In the same way using sulfation products of a ers as shown. C8 fraction 0f cracked Wax olens as feed, a yield 165 While the cascade now apparatus just described Of SecOndaIY Octyl alcohol 0f abOut 75% 0f the is preferred for carrying out the new process of theoretical based on the monoand di-alkyl sulthe invention because this improved apparatus fates going into reactor I is obtained, the crude oifers particular advantages in regard to conproduct recovered via line 2| being secondary struction and operating costs, nevertheless, other octyl alcohol, boiling 179 C., containing Cs hy- 70 suitable forms of apparatus maybe used in the process. Thus, for instance, pumping means may replace the hydrostatically balanced cascade system for the transfer oi? liquid mixture from re- I valve-controlled pipe 7 lines may be used .for such 'transfer of liquid mixture, the control valves in the transfer lines being regulated by lliquid level indicating means in reactors '2 and 3 so as to yinsure the desired hold-up of oily layer relative to aqueousv acid layer therein. The process described can also, if desired, be modified by carrying out a limited steam distillation in reactor I. In this case the reflux condenser 23 would be replaced by a vapor off-take similar to the pipe 116 and cyclone I1, and likewise connected with the vapor line I8. As mentioned above, this would increase the residence time of the `oily 'layer in reactors 2 and 3. Indirect heating instead of steam injection in reactor- I is also feasible, particularly when no distillation is carried out 1n this reactor. I

It will thus be seen that 'the process of the 1nvention is capable of considerable variation not only in regard to the methods of operation which may be used but also Ain respect to the nature of the ester mixtures which may be treated. Thus, for example, instead of acid `mixtures of monoand di-alkyl sulfates, one may successfully treat in the same way mixtures of thecorresponding monoand `di-alky'l phosphates or mixtures of mono, diand tri-alkyl phosphates, Still other variations in the process `may be made without departing `from the invention, and it will be understood that neither the new `process nor the improved apparatus which has been provided is limited to the details disclosed by way of eX- ample nor by any theory proposed in 'explanation of the improved results which are obtained.

I claim as my-inven'ti'on:

1. A process for the production of alcohols which are sparingly soluble in water and are `volatile in steam by acid hydrolysis .of .a mixture of the corresponding monoand poly-esters of la polybasic rinorganic acid, which comprises heating said mixture of esters'in the presence'ofldilute aqueous inorganic acid to effect hydrolysis of at least a major part of the said mono-ester, passing the resulting mixture containing an oily phase comprising said poly-ester and an aqueous acid phase through a hydrolysis zone wherein said phases are at least partially separated and the aqueous phase is withdrawn at a faster rate than said oily phase to provide a longer residence time in the second of said hydrolysis zones for said poly-ester than for said aqueous acid'phase. and subjecting the oily phase in said hydrolysis zone to heating with steam to bring about hydrolysis of at least a substantial part of said polyester content of the oily phase and to lvaporize and remove alcohol therefrom.

2. A process for the production of alcohols sulfate, 4continuously withdrawing aqueous Aacid jphase in said 'second'rea'c'tortosteamuistillation to `remove alcohol therefrom as vapor and brins about hydrolysis of di-alkyl sulfate.

3. A process for the production of secondary aliphatic alcohols of 7 to 9 carbon atoms per molecule from a mixture of the corresponding monoand di-alkyl esters cf an inorganic polybasic acid, which comprises heating said mixture of esters in the presence of a dilute aqueous solution of a strong inorganic polybasic acid to effect sufficiently complete hydrolysis of the mono-alkyl ester content to substantiallysuppress the frothing tendency of lthe mixture, and subjecting the resulting product to steam distillation to remove alcohol therefrom -while simultaneously withdrawing from the mixture an `oily upper layer and an aqueous acid lower layer, the rate of Withdrawal of said acid layer being more rapid than .the rate of withdrawal of said oily layer. whereby a longer residence time is provided for said oily layer than for said acid layer and hydrolysis of di-alkyl ester in said oily layer is effected.

4. A process for the production of an aliphatic alcohol having 5 to 12 carbon atoms per molecule from a mixture of monoand di-alkyl sulfates .of said alcohol, which Acomprises heating said mixture in the presence of sulfuric acid of 15% to 30% concentration on an organic-free basis for a vperiod of 15 to 60 minutes to substantially hydrolyze the mono-alkyl sulfate content, passing the thus reacted mixture to a second hydrolysis zone ,wherein the mixture is separated into two liquid phases, an aqueous sulfuric acid phase and an oily vphase containing the di-alkyl sulfate, injecting steam into the mixture to effect steam distillation of the alcohol present and bring about khydrolysis of said di-alkyl sulfate, and withdrawing from said second hydrolysis zone liquid oily ,phase and aqueous acid phase at rates controlled so that the oily phase has a materially longer residencetime in the hydrolysis zone than said aqueous acid phase whereby hydrolysis of the dialkyl sulfate is effected without substantial convers1on vof alcohol to undesirable by-products.

5. A process according to claim 4-wherein the di-alkyl sulfate-containing oily phase is 'main- .tamed under hydrolysis conditions for at least 4 hours.

6. A process for the production of a secondary ahphatic alcohol having 7 to 9 carbon atoms per molecule from a mixture of monoand Idi-alkyl sulfates of said alcohol, which ,comprises heating vsaid mixturein the presence of dilute aqueous sulfuric acid at C. to 120 C. until substantial hydrolysis of said mono-alkyl sulfate takes place, passing the reacted mixture to a hydrolyr wherein separation of the mixture into an oily ,llquid phase containing dialkyl sulfate and an aqueous sulfuric acid phase takes place controlling the rates of withdrawal of liquid oily phase and aqueous acid phase so as to maintain said olly phase under hydrolysis 4conditions for a -substantially longer .period than said aqueous acid phase whereby hydrolysis. of the dialkyl sulfateis effected withoutsubstantial lconversion of alcohol undesirable byfproducts, and simultaneous. s eam distil in phasey l g ofi" alcohol from the oily "7. Aprocess for the production of alcohol as-ulfation product of oleflns having 5 to lsZfzxII "bon atoms per molecule containing monoand liii-alkyl -sulfates and free sulfuric acid, which comprises diluting said sulfation product with sufficient water Vtoreduce the sulfuric acid concentration so as not to exceed 30% on'an organicfree basis after complete hydrolysis of the esters, heating the diluted mixture to substantially hydrolyze the mono-alkyl sulfate content, passing the thus reacted mixture through a hydrolysis Zone wherein separation of an oily liquid phase containing di-alkyl sulfate from an aqueous acid phase is effected, withdrawing from said zone separated aqueous acid phase at a faster rate than oily liquid phase, and simultaneously steam dstilling said oily phase to remove alcohol therefrom and hydrolyze di-alkyl sulfate without substantial conversion of the alcohol produced to undesirable by-products.

8. A continuous process of hydrolyzing an acid mixture of monoand cli-alkyl sulfatos, which comprises passing said mixture through at least two separate hydrolysis zones in series, maintaining' the mixture in the iirst zone at an elevated temperature and -for a time at which substantial hydrolysis of the mono-alkyl sulfate content takes place While avoiding substantial phase separation, separating the mixture in the second Zone into a liquid oily phase containing di-allryl sulfate and an aqueous acid phase, injecting steam into said mixture in said second zone to eiect hydrolysis of di-alkyl sulfate and distill oi alcohol therefrom, and withdrawing from said second reaction zone liquid oily phase and aqueous acid phase at rates controlled so that the average residence time of liquid oily phase is greater than the average residence time of aqueous acid phase therein whereby hydrolysis of the dialkyl sulfate is effected without substantial conversion of alcohol to undesirable by-products.

LESLIE NEWTON GOLDSBROUGH.

References Cited in the ille of this patent UNITED STATES PATENTS Number Name Date 1,915,820 Enge et al. June 27, 1933 2,014,078 Archibald et a1. Sept. 10, 1935 2,096,878 Brooks Oct. 26, 1937 2,160,177 Shuman May 30, 1939 2,-i7tl,569 Bannon June 28, 1949 2,475,095 Hoek July 5, 1949 2,496,251 Mottern Jan. 31, 1950 

1. A PROCESS FOR THE PRODUCTION OF ALCOHOLS WHICH ARE SPARINGLY SOLUBLE IN WATER AND ARE VOLATILE IN STREAM BY ACID HYDROLYSIS OF A MIXTURE OF THE CORRESPONDING MONO-AND POLY-ESTERS OF A POLYBASIC INORGANIC ACID, WHICH COMPRISES HEATING SAID MIXTURE OF ESTERS IN THE PRESENCE OF DILUTE AQUEOUS INORGANIC ACID TO EFFECT HYDROLYSIS OF AT LEAST A MAJOR PART OF THE SAID MONO-ESTER, PASSING THE RESULTING MIXTURE CONTAINING AN OILY PHASE COMPRISING SAID POLY-ESTER AND AN AQUEOUS ACID PHASE THROUGH A HYDROLYSIS ZONE WHEREIN SAID PHASES ARE AT LEAST PARTIALLY SEPARATED AND THE AQUEOUS PHASE IS WITHDRAWN AT A FASTER RATE THAN SAID OILY PHASE TO PROVIDE A LONGER RESIDENCE TIME IN THE SECOND OF SAID HYDROLYSIS ZONES FOR SAID POLY-ESTER THAN FOR SAID AQUEOUS ACID PHASE, AND SUBJECTING THE OILY PHASE IN SAID HYDROLYSIS ZONE TO HEATING WITH STEAM TO BRING ABOUT HYDROLYSIS OF AT LEAST A SUBSTANTIAL PART OF SAID POLYESTER CONTENT OF THE OILY PHASE AND TO VAPORIZE AND REMOVE ALCHOL THEREFROM. 